Polyepoxides from disulfonamides,, process therefor and cured products therefrom

ABSTRACT

Novel polyepoxides are prepared from a disulfonamide such as diphenylether disulfonamide, epihalohydrin and sodium hydroxide with the use of 10 or more moles of epihalohydrin per mole of disulfonamide. These novel polyepoxides can be thermoset by heating either in the presence or absence of the usual catalysts or curing agents.

United States Patent Smith PM Apr. 8, 1975 POLYEPOXIDES FROMDISULFONAMIDES,, PROCESS THEREFOR [56] R f ren e Cited AND CUREDPRODUCTS THEREFROM UNITED STATES PATENTS [751 lnvemo Smith 2.643.2446/l953 Simons 260/47 x 731 Assignees: David P. sheen. both of Midland2.671.771 2/1954 Kenson 260/47 Mich; The Dow Chemical Dbl-.895 l../l96lReynolds ..60/348.6 X Company, Midland. Mich. Primary E.\'aminerLesterL. Lee [22] FIed: May I973 Attorney Agent. or Firm-Benjamin G. Colley[2]] Appl. No.: 363,204

Related US. Application Data ABSTRACT [63] Continuation-impart of Ser.No. 236.473. March 20. Novel polyepoxides are prepared from a disulfona-1972. abandoned. mide such as diphenylether disulfonamide. epihalohydrinand sodium hydroxide with the use of 10 or more C| 117/161 260/47 EP;moles of epihalohydrin per mole of disulfonamide. 260/63 l 260/830 P;These novel polyepoxides can be thermoset by heating 260/857 R either inthe presence or absence of the usual catalysts [51] Int. Cl. C08g 20/36o curing agents, [58] Field of Search 260/97 ED. 49, 2 ED, 79,

260/793 M. 830 P. 857 R 16 Claims, No Drawings CROSSREFERENCE TO RELATEDAPPLICATIONS This application is a continuation-in part of Ser. No.236,473. filed on Mar/20, 1972 and now abandoned.

BACKGROUND OF THE INVENTION wherein A is a divalent hydrocarlmn grouphaving from 1 to about 6 carbon atoms.

9 Q l? -o-, -c-, -s-, -s-, -s-, or -s-s-,

n has a value of 0 or 1: or

This invention relates to novel polyepoxides prepared fromdisulfonamides. a process for their preparation and cured productsthereof.

It is known from the patent to Simons US. Pat. No. 40 2,643,244 thatsulfonamides can be reacted with epichlorohydrin to producethermoplastic resins having little or no residual epoxy groups and thatthese resins are useful to make coatings when modified with linseed oilacids and the like. In contrast to this. the present in- 45 ventionproduces resins having an average of more than one epoxide group permolecule and are thermosettable with the usual catalysts or curingagents.

SUMMARY OF THE INVENTION wherein in the above formulae I through I\"each R is independently hydrogen or the group CH- CHOHCH. Z wherein Z isCl. Br or I; each R is independently hydrogen; an aliphatic hydrocarbongroup having 1-6 carbon atoms: Cl; Br; or OR wherein R is an acyl grouphaving 16 carbon atoms. In and m have values of from 0 to 2, with theproviso that the sum of m and m is a value greater than about 1.5 andpreferably a value between about 1.8 to about 2.3.

While the foregoing formulae are believed to be an accuraterepresentation of the polyepoxides of this invention, there may also bea minor amount of dimers of an unknown structure present in thepolyepoxides of.

this invention.

The novel polyepoxides of the present invention are useful as moldingresins and coatings. useful to make reinforced plastics and pottingcompositions and the like.

DETAILED DESCRIPTION preferably from about 4 to about 6 hours in thepresence of a slight stoichiometric excess of an alkali or alkalineearth metal hydroxide or carbonate, alkaline earth metal oxides ormixture thereof. thereafter removing the excess epihalohydrin andrecovering the desired polyepoxide.

An excess of an epihalohydrin. for the purposes of this invention. isdefined as 10 or more moles per mole of the disulfonamide and preferablyin the range of from 10:1 to :1.

Suitable disulfonamides which are employed to produce the novelpolyepoxides of the present invention include those representedby thegeneral formulae:

II II )@'S-NH= and II n I o 0 II I am s s an, II II o 0 VII. 0 0

II II am s w s an, and

II 0 R: X R: 0

VIII.

N I a 5 Q5 NH: II II 0 o 'para-phenylene disulfonamide. dibenzofu randisulfonamide. thereof. and the like.

dibenzothiophene disulfonamide. mixtures Suitable epihalohydrins whichare employed in the process of the present invention includeepichlorohydrin. epibromohydrin. epiiodohydrin. mixtures thereof and thelike.

Suitable alkali and alkaline earth metal hydroxides include sodiumhydroxide. potassium hydroxide. calcium hydroxide. barium hydroxide,mixtures thereof and the like.

Suitable alkali and alkaline earth metal carbonates include sodiumcarbonate. potassium carbonate, barium carbonate. calcium carbonate.magnesium carbonate. mixtures thereof and the like.

Suitable alkaline earth metal oxides include barium oxide. calciumoxide. magnesium oxide. mixtures thereof and the like.

The excess epihalohydrin is conveniently removed by any of the wellknown methods such as for example. flashing at elevated temperature andreduced pressure, extraction with liquid aliphatic hydrocarbons, e.g.,pentane or hexane. combinations thereof and the like.

The polyepoxide product is conveniently recovered by any of the wellknown methods of polymer recovery such as. for example. solventextraction. with subsequent evaporation of the solvent. water washing.combinations thereof and the like.

The disulfonamide starting materials are conveniently prepared bychlorosulfonating the desired aromatic compound with at least astoichiometric quantity of a suitable chlorosulfonation agent such as.for example. chlorosulfonic acid at a temperature of from about 50C. toreflux for from about 2 to about 6 hours or longer. The resultantdisulfonyl chloride after removal of any excess chlorosulfonation agentis then reacted with aqueous or anhydrous ammonia at reflux temperaturefor about 10 to about 24 hours. If desired. the disulfonyl chloride canbe reacted with ammonia under autogeneous pressure at C in about 1 to 2hours. The resultant disulfonamide is then precipitated in cold water.filtered. and the product is finally recovered by slurrying theprecipitate in hot water and again filtering.

The compositions of the present invention are believed to be mixtures ofpolyepoxides and in as much as the particular position of thesulfonamide groups or a substituent on the aromatic ring is not believedto be of any particular concern. no attempts have been made to determinesuch positions. What is important. is that the polyepoxides of thepresent invention have more than one epoxy group per molecule. However.the sulfonamide groups are usually in the 4.4'-positions when a diphenylether is employed and the 1,5-positions when a naphthalene is employed.The compositions may include amounts of other known polyepoxides. suchas the diglycidyl ether of bisphenol A.

Suitable catalysts and curing agents which are employed to cure thepolyepoxides of the present invention include the well known epoxycatalysts and curing agents such as primary. secondary and tertiaryamines, polybasic acids and anhydrides. polyamides, Lewis acids.mixtures thereof and the like.

The type and quantity of catalyst and/or curing agent employed dependsupon the physical properties desired of the cured product.

lnert fillers. fire retardant agents. accelerators. extenders and othermodifiers may be added to the compositions of the present invention tomodify the properties thereof.

The following examples are illustrative of the present invention and arenot to be construed as to limiting the scope thereof in any manner.

EXAMPLE 1 To a reaction vessel equipped with a stirring means,temperature control means, refluxing means and vacuum means was added32.8 grams (0.] mole) of diphenylether-4.4'-disulfonamide. 92.5"g. 1.0mole) of epichlorohydrin and 2.5 ml. of water. After raising thetemperature to 95C. with stirring. 8.8 g. (0.22 mole) of pelletizedsodium hydroxide was added and the contents of the vessel was refluxedat 108C. with stirring for 6 hours. The excess epichlorohydrin wasremoved by vacuum flashing at 50C. and 1 mm. Hg. The product was thenrecovered by two extractions with 250 ml. each of warm acetone andsubsequent removal of the acetone at 40-50C. and mm. Hg. There wasrecovered 44 grams of colorless gummy polyepoxide having an epoxideequivalent weight (E.E.W.) of 218 and an epoxy functionality of 2.06which was soluble in acetone and pyridine. 7

In order to illustrate the unexpected differences of this invention overthe prior art i.e. the Simons patent. U.S. Pat. No. 2,643,244, Example 3of this patent was repeated using diphenyl ether disulfonamide insteadof N.N'-n-butyl diphenyl ether and the maximum ratio of epichlorohydrinto diphenyl ether disulfonamide (6:1) taught by Simons.

The results are tabulated and compared along with the results fromExample 1 above in Table 1.

Table 1 Reagents Ex. 3 of 2.643.244 Ex. 1

diphenyl ether disul- 1 1.2 gms.(0.03-1 32.8 grns. fonaniide (DPEDSA)mole) (0.1 mole) epiclilorohydrin (Epi) 18.9 gms. 92.5 gms.

(0.204 mole) 1.0 mole) EXAMPLE 2 In a procedure similar to Example 1.several resin preparations were made employing a mole ratio ofdisulfonamide/NaOH/epichlorohydrin of 1/22/10 employing various reactiontemperatures and time. The

conditions and times are given in the following Table l1.

for comparative purposes while Experiments C. D and E were examples ofthe present invention.

EXAMPLE 3 2.5 Grams of the product of Example 1 was mixed with astoichiometric quantity (0.2 grams) of diethylene triamine and cured atvarious temperatures. The results are given in Table 111.

For comparative purposes, 500 grams ofa diglycidyl ether of bisphenol A(DGEBA) having an EEW of about 189 was also cured with a stoichiometricquantity of diethylene triamine (DETA). The results are given in Table111.

Table 111 Cure Gel Time Cure Time Resin Temperature Minutes (Time toHarden) DGEBAI- ambient (25C) 30-60 24:48 hours DETA 4 DGEBAI- C ND l'2hours DETA Ex. l/DETA ambient (25C) 3 25 minutes Ex. l/DETA 100C 1.25810 minutes Ex. l/DETA C 1 1 minute ND not determined I The aboveexample demonstrates that the polyepoxides of the present invention cureat a faster rate than the polyepoxides of the glycidyl ether of abisphenol type.

EXAMPLE 4 A 2 gram portion of the polyepoxide prepared in Example l washeated-at a temperature of 150C in the absence of catalyst or hardener.The resin gelled within 45 minutes and washard within 2V2-3 hours.

We claim:

1. A polyepoxide represented by the formulae 5 wherein A is a divalenthydrocarbon group having from 1 to about 6 carbon atoms,

o O wherein: u n u A is a divalent hydrocarbon group having from 1 to5.-, -s-, r about 6 carbon atoms,

O O 5 II 9 9 -o-, -c-, -s-, -s-, -s-, or -s-s-;

, n n has a value of 0 or 1; or O rm 0*) r ,0. 9 l? ,0. (CH:- H-Cl'lfia-N PQQ- s u -(cn,-ca-ct1=) or n n m 0 O (Ifh-m o o (l t),-m' III. /o\ IIll 1 =-CH-CH=)N -s s N (ca at-cm) m I u m R R wherein X is oxygen orsulfur; or n has a value of O or 1; R' is independently hydrogen; analiphatic hydrocarbon group having l-6 carbon rm (R) -m' atoms; Cl; Br;or -OR wherein R is an acyl group o o n u ,0\ having 1-6 carbon atoms;and X is oxygen or sula- H- fi -N fi N (CHQ-CH-CHI) 1,25 fur;

0 o is reacted with a stoichiometric excess of an epihalohydrin at atemperature of from about 70C. to reflux R temperature for at least 3hours in the presence of ".1

wherein in the above formulae 1 through [V each R is independentlyhydrogen or the group CH- CHOH13 CH- ,Z wherein Z is Cl. Br or I; each Ris independently hydrogen; an aliphatic hydrocarbon group having 1-6carbon atoms; Cl; Br; or -OR;; is an acyl group having 1-6 carbon atoms;In and m have values of from 0 to 2. with the proviso that the sum of mand m is a value greater than about 1.5.

2. A polyepoxide of claim 1 wherein the sum of m and m has a value fromabout 1.8 to about 2.3.

3. A polyepoxide of claim 1 as represented by Formula 1 wherein n has avalue of l.

4. A polyepoxide of claim 3 wherein A is O. and the sum of m and m isabout 2.

5. A process for preparing the polyepoxide composition of claim 1wherein a disulfonamide selected from the formulae slight stoichiometricexcess of an alkali or alkaline earth metal hydroxide or carbonate oralkaline earth metal oxide or mixture thereof and thereafter recoveringthe polyepoxide product.

6. The process of claim 5 wherein the time of reaction is from about 4to about 6 hours at a temperature of from about C. to reflux.

7. A thermosettable composition comprising a polyepoxide of claim 1 anda curing amount ofa curing agent or a catalytic amount of a catalyst.

8. A thermosettable composition comprising a polyepoxide of claim 3 anda curing amount ofa curing agent or a catalytic amount of a catalyst.

9. A thermosettable composition comprising a polyepoxide of claim 4 anda curingamount ofa curing agent or a catalytic amount of a catalyst.

10. The product resulting from heating the composition of claim 7.

11. The product resulting from heating the composition of claim 8.

12. The product resulting from heating the composition of claim 9.

13. The product resulting from heating a composition comprising apolyepoxide of claim 1 as the sole source of Vic-epoxy groups.

14. The product resulting from heating a composition comprising apolyepoxide of claim 3 as the sole source of Vic-epoxy groups.

15. The product resulting from heating a composition comprising apolyepoxide of claim 4 as the sole source of vie-epoxy groups.

16. The process of claim 5 wherein the disulfonamide is reacted with a10 to 20 molar excess of an epihalohydrin.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 9 DATEDApril 8, 1975 INVENTOMS): Harry A. Smith, David P. SheetzHiscaflfiedmatamrammaminmeamwe-memfiwdpamntmdfiwtsmdLeflmsPammmehembyconededasshownbdow:

On first page please correct the assignee section, the

inventor David P. Sheetz, should be on the Inventor line.

Col. 7, line 6, please add -S-S; before the phrase "n has a value of Oor 1; or?

Col. 7, line 31, please delete in the formula -l3.

Col. 7, line 33, please add after 0R wherein R Signed and Emalcd thisseventeenth Day of February1976 [SEAL] Attest:

C. MARSHALL DANN Arresting Officer

1. A POLYEPOXIDE REPRESENTED BY THE FORMULAE
 2. A polyepoxide of claim 1wherein the sum of m and m'' has a value from
 3. A polyepoxide of claim1 as represented by Formula I wherein n has a
 4. A polyepoxide of claim3 wherein A is --O--, and the sum of m and m'' is
 5. A process forpreparing the polyepoxide composition of claim 1 wherein a disulfonamideselected from the formulae
 6. The process of claim 5 wherein the time ofreaction is from about 4 to
 7. A thermosettable composition comprising apolyepoxide of claim 1 and a
 8. A thermosettable composition comprisinga polyepoxide of claim 3 and a
 9. A thermosettable compositioncomprising a polyepoxide of claim 4 and a
 13. The product resulting fromheating a composition comprising a
 14. The product resulting fromheating a composition comprising a
 15. The product resulting fromheating a composition comprising a
 16. The process of claim 5 whereinthe disulfonamide is reacted with a 10 to 20 molar excess of anepihalohydrin.